Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable catalyst for Suzuki-Miyaura coupling reaction in water

Article abstract of DOI:10.1016/j.molcata.2014.09.009

Palladium nanoparticles were supported on magnetic Fe₃O₄/reduced-graphene oxide(Fe₃O₄/r-GO)nanohybrid by reduction of dichloropalladium (II) complex in water. Pd/Fe₃O₄/r-GO nanohybrid wasch

Full text of DOI:10.1016/j.molcata.2014.09.009

Accepted Manuscript
Title: Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid
as an efficient and recoverable catalyst for Suzuki-Miyaura
coupling reaction in water
Author: S. Jafar Hoseini Vahid Heidari Hasan Nasrabadi
PII:
S1381-1169(14)00412-9
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2014.09.009
MOLCAA 9270
To appear in:
Journal of Molecular Catalysis A: Chemical
Received date:
Revised date:
Accepted date:
24-6-2014
4-9-2014
5-9-2014
Please cite this article as: S.J. Hoseini, V. Heidari, H. Nasrabadi, Magnetic
Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable catalyst
for Suzuki-Miyaura coupling reaction in water, Journal of Molecular Catalysis A:
Chemical (2014), http://dx.doi.org/10.1016/j.molcata.2014.09.009
This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.

Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable
catalyst for Suzuki-Miyaura coupling reaction in water
S. Jafar Hoseini, Vahid Heidari and Hasan Nasrabadi
Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj, 7591874831, Iran
Abstract
Palladium nanoparticles were supported on magnetic Fe3O4/reduced-graphene oxide(Fe3O4/r-
GO) nanohybrid by reduction of dichloropalladium (II) complex in water. Pd/Fe3O4/r-GO
nanohybrid was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray
diffraction, and transmission electron microscopy (TEM). Our study shows that Pd/Fe3O4/r-GO
nanohybrid was suitable for Suzuki-Miyaura carbon-carbon coupling reaction in water.
Compared to the classical reactions, this method consistently has the advantages of green
solvent, short reaction times, little catalyst loading, high yields, easy magnetically separation and
reusability of the catalyst. Furthermore, Pd/Fe3O4/r-GO nanohybrid shows a high catalytic
activity toward aryl chloride derivatives.
Keywords: Magnetic nanohybrid, Suzuki-Miyaura reaction, Carbon-carbon coupling, Catalyst
1. Introduction
Nano-scale palladium particles make them attractive in catalysis due to their large surface
area. Several palladium nanoparticles (NPs) as catalysts for carbon-carbon coupling reactions
such as the Suzuki-Miyaura reaction have been reported [1-3].
In recent decade, as an important family of separation materials, magnetic Fe3O4 NPs have
attracted considerable interest in chemistry and material sciences, due to their potential

Corresponding author, E-mail: jhosseini@yu.ac.ir; Tel: +98 7412223048, Fax: +98
7413342172
1
Page 1 of 23

applications in catalysis and biomedicine [4]. The paramagnetic and insoluble properties of
Fe3O4 NPs enable the catalyst to be easily separated with an external magnetic field. Fe3O4 NPs,
in particular, are environmentally benign, economic and comparatively non-toxic [5]. Recently,
magnetic NPs were used as an efficient catalyst in many organic reactions [6-8]. However, to
realize the successful applications of these magnetic NPs, at least two aspects need to be
considered. First, the magnetic properties, which usually depend on several factors such as size,
size distribution, shape and the chemical/biological stability of iron oxide NPs, should be
improved. Second, these inherently instable NPs should be stabilized by matrix materials and the
aggregation of Fe3O4 NPs due to strong magnetic dipole–dipole attractions between particles
must be reduced.
Graphene is one-atom-thick layer of sp2 hybridized carbon tightly packed into a two
dimensional honeycomb lattice, and is a basic building unit for graphitic materials of all other
dimensionalities [9]. Recently, many types of metal oxides NPs such as Fe3O4 [10], Co3O4 [11],
TiO2 [12] and ZnO [13] could be deposited on graphene oxide (GO) sheets to impart new
functionality to this increasingly popular 2D nanomaterials in consideration of its large surface
area.
Palladium catalyzed Suzuki cross-coupling reaction between an aryl halide and a phenyl
boronic acid has been among the most powerful tools for constructing carbon–carbon bonds in
organic synthesis [14]. Because biaryl moieties are used as the building block of a wide range of
pharmaceuticals, herbicides, natural products, polymers, and etc, much effort has been spent on
the development of simple and practical conditions for the Suzuki–Miyaura coupling reaction
[15]. Generally, phosphine ligands are often used in Pd-catalyzed processes, but most of them
are toxic, expensive and water or air sensitive [16]. Recently, employing readily available aryl
2
Page 2 of 23

chlorides in these transformations have received increasing attention, and a number of effective
catalytic systems have been developed for this purpose [17-18].
In this study, a successful method has been demonstrated for the synthesis of magnetic
Pd/Fe3O4/reduced-graphene oxide (r-GO) nanohybrid. Then, Pd/Fe3O4/r-GO nanohybrid is used
as non-phosphine catalyst for Suzuki-Miyaura reaction in water. This catalyst showed two main
advantages in studying of its catalytic activity for Suzuki-Miyaura reaction. First, it has high
surface area due to both Pd NPs and r-GO sheets, so the contact between reactants and catalyst
increases considerably. Second, due to their insolubility in the reaction mixture and paramagnetic
properties of Pd/Fe3O4/r-GO nanohybrid, they can be separated easily from the reaction mixture
by applying an external magnet. Recently, we have investigated thin film formation of Pd/r-GO
and Pd NPs at oil-water interface as effective catalyst for Suzuki-Miyaura reaction in water [19].
In comparison to the previous work, although Pd loading decreased in this work but reaction
between aryl halides and phenyl boronic acid performed in higher isolated yields at less times.
2. Experimental
All of the chemical compounds were purchased from Merck Company. The powder X-ray
diffraction patterns (XRD) were obtained by a Bruker AXS (D8, Advance) instrument
employing the reflection Bragg–Brentano geometry with Cu-Kα radiation. Transmission electron
microscopy (TEM) images were taken with a Philips CM-10 microscope operated at 100 kV.
1
The FT-IR spectra were taken with a Jasco FT/IR-680 plus spectrometer. H NMR spectra were
taken with a Bruker 400 MHz Ultra-shield spectrometer using CDCl3 as the solvent and TMS as
the internal standard. Ultrasonication was performed in a TECNO-GAZ Tecna 3 ultrasonic bath.
3
Page 3 of 23

2.1. Preparation of GO
GO was prepared using modified Hummers method from flake graphite (Merck Company)
[20]. Briefly, a flask containing 1 g of graphite and 0.75 g of NaNO3, was placed in the ice-water
bath. 75 mL of H2SO4 was added with stirring and then 4.5 g of KMnO4 were slowly added over
about 1 h. After the mixture was stirred vigorously for 5 days at room temperature, 140 mL 5 %
H2SO4 aqueous solution was added over about 1 h with stirring , and the temperature was kept at
°
°
98 C. The temperature was reduced to 60 C, 3 mL of H2O2 (30 wt% aqueous solution) was
added, and the mixture was stirred for 2 h at room temperature. As-prepared GO was suspended
in ultra-pure water to give a brown dispersion, which was subjected to dialysis to completely
remove residual salts and acids. Resulting purified GO powders were collected by centrifugation
and air-dried. GO powders were dispersed in water to create 0.05 wt% dispersion. Then, the
dispersion was exfoliated through ultrasonication for 1 h, which the bulk GO powders were
transformed into GO nanoplatelets.
2.2 Preparation of Fe3O4 NPs
To prepare Fe3O4 NPs, 5.2 g of FeCl3 and 2.0 g of FeCl2 were successively dissolved in 25
mL of distilled water containing 0.85 mL of 12.1 N HCl. The resulting solution was added
dropwise into 250 mL of 1.5 M NaOH solution under vigorous stirring. The last step generated
an instant black precipitate. The precipitate was isolated in the magnetic field, and the
supernatant was removed from the precipitate by decantation [6f].
2.3 Preparation of Fe3O4/γ-Aminopropyltriethoxysilane (APTES)
In order to coat the Fe3O4 NPs with APTES, NPs were ground into powder in an agate mortar
and placed in a clean and dry round-bottom flask. To this, 20 mL of dry toluene was added and
the mixture placed in a sonic bath for 30 minutes. The APTES reagent was added to the Fe3O4
4
Page 4 of 23

NPs at a 1:1 molar ratio from a micropipette in a nitrogen atmosphere. The mixture was stirred at
60 °C for 12 h after which the mixture was cooled down and the residue washed with dry toluene
and then with a water-acetone mixture (20% of H2O). The functionalized Fe3O4 NPs were dried
under vacuum for one day at ambient temperature [21].
2.4 Preparation of Fe3O4/GO nanohybrid
0.02 g of GO was dispersed in distilled water and placed in a sonic bath for 10 minutes.
Finally, a mixture contains 0.02 g Fe3O4/APTES and 0.02 g NaOH in water was added. The
reaction mixture was heated under a reflux condenser in the presence of N2 gas at 80 °C for 24 h.
2.5 Preparation of Pd/Fe3O4/r-GO nanohybrid
0.01 g of Fe3O4/GO was dispersed in 2 mL of distilled water and placed for 1 hour under
ultrasonic waves. Subsequently, a solution contain PdCl2 (0.14 mmol) dissolved in HCl was
added. Finally, 0.1 g of NaBH4 was added slowly to the resulting mixture and refluxed for 12 h
at 60 °C under nitrogen atmosphere. The isolated solid was dried at room temperature for 24 h in
vacuum. The solid contained 0.54% Pd by weight based on the inductively coupled plasma (ICP)
analysis.
2.6 General procedure for Suzuki-Miyaura coupling reaction
Arylhalide (1 mmol) and phenyl boronic acid (1.5 mmol) were added to a flask containing the
Pd/Fe3O4/r-GO catalyst (0.36 mol% of Pd) and K2CO3 (2 mmol) in distillated water (5 mL). The
°
mixture was stirred in an oil bath at 80 C. After completion of the reaction (monitored by TLC),
the reaction mixture was cooled down to room temperature and then, dichloromethane (5×10
mL) was added to the reaction vessel and separated solid catalyst by a normal magnet. The
organic phase was separated and dried over anhydrous MgSO4. Evaporation of the solvent gave
the pure desired product. Characterization of these compounds was established by comparison of
5
Page 5 of 23

1
their H NMR spectra with those of authentic sample and the details are given in the supporting
information.
3. Results and Discussion
The Fe3O4/GO nanohybrid synthesized according to procedure titled in the experimental
section and graphically summarized in Scheme 1.
Scheme 1. Picture shows the synthesis of Fe3O4/GO nanohybrid.
FT-IR spectra of GO, Fe3O4/APTES and Fe3O4/APTES/GO supplied in the supporting
information (Figure S1). The results from FT-IR spectroscopy revealed that the characteristic
band of the carboxyl group in GO appears at ca. 1731cm-1 (C=O stretching) (Figure S1a) [22,
23]. The C–O vibrations of epoxy groups in GO appeared at ca. 1124 cm-1 [22, 24].
As shown in Figure S1b, the peaks at 2865 cm-1 and 2924 cm-1 corresponds to symmetric νs
CH2 and asymmetric νas CH2 of the alkyl chains, respectively, and is assigned to APTES. The
absorbance band at 588 cm-1 ascribed to Fe2+-O2- vibration and is consistent with the reported IR
spectra for spinel Fe3O4 [6f]. Moreover, appearance of the bands at ca. 1128 cm-1 (ν Si–O–C)
provides more evidence for the presence of APTES [25]. The FT-IR result in Figure S1c shows
that Fe3O4/APTES/GO nanohybrid is formed via a SN2 nucleophilic displacement reaction
between epoxy groups of GO and amino moieties of Fe3O4/APTES NPs. Amine groups did not
6
Page 6 of 23

reacted with carboxylic acid groups of GO through the amidation process because the amide ν
NH vibration expected at 3300 cm-1 is not present and the 1650–1750 cm-1 region does not show
a strong ν C=O band. The absorption band at around 1700 cm-1 is attributed to the carboxyl
groups. However, the corresponding absorption (Figure S1c) at this range is not observable,
likely due to the overlapping of absorption of graphene sheets in this region [22]. Figure 1 shows
a TEM image of Pd/Fe3O4/r-GO nanohybrid. In this image, Pd/Fe3O4 NPs appear as spherical
particles with diameters of about 3 nm on a lighter shaded substrate corresponding to the planar
r-GO sheets.
Figure 1. TEM images show (a and b) spherical Pd/Fe3O4/r-GO nanohybrid with 2-3 nm and (c)
the Histogram of particle size distribution.
In the XRD pattern of Pd/Fe3O4/r-GO nanohybrid (Figure 2) four clear diffraction bands
centered at 2θ of 40.2°, 46.6°, 68.1° and 82.1°,correspond to the (111), (200), (220) and (311)
crystalline planes of Pd, respectively [26]. The weak diffraction peaks identified by # symbol
correspond to the (220), (311), (400), (422), (511) and (440) planes of Fe3O4 lattice, respectively
[6g]. r-GO shows a broad diffraction peak for C (002) at 2θ = 28° similar to that of carbon black
[27].
7
Page 7 of 23

Figure 2. XRD pattern of Pd/Fe3O4/r-GO nanohybrid.
Figure 3 shows the results for magnetization as function of applied field at room temperature
obtained for dry powder of Pd/Fe3O4/r-GO nanohybrid. Magnetic measurement indicates
magnetic behavior at room temperature for Pd/Fe3O4/r-GO nanohybrid with no hesteresis and
perfect Langevin behavior. For Pd/Fe3O4/r-GO nanohybrid, the saturation magnetization value
(Ms) is 5.9 emu/g, which was lower than that of pure Fe3O4 NPs. There are numerous routes that
can explain the reduction of the Ms for coated magnetic NPs. In this case, the presence of
nonmagnetic APTES and r-GO on the surface of Pd/Fe3O4/r-GO lead to decrease of the Ms.
8
Page 8 of 23

Figure 3. Room-temperature magnetization curve of magnetic Pd/Fe3O4/r-GO nanohybrid.
3.1. Characterization of Suzuki-Miyaura reaction
Pd/Fe3O4/r-GO nanohybrid is used as an efficient recoverable catalyst in the Suzuki-Miyaura
coupling reaction. As shown in Scheme 2, reaction of aryl halide and phenyl boronic acid in
water was investigated in the presence of Pd/Fe3O4/r-GO nanohybrid as catalyst.
K2CO3 , 2mmol
H2O (5 mL)
Reflux
G
G
B(OH)2
+
Pd/Fe3O4/r-GO
X
G = H, Me, CN, NO2
. Pd/Fe O /r-GO nanohybrid catalyzed Suzuki-Miyaura coupling reaction of aryl
Scheme 2
3
4
halides with phenyl boronic acid in water.
The experiments with different solvents were rather performed to find the best medium for the
coupling in the presence of the Pd/Fe3O4/r-GO nanohybrid catalyst. According to the results
shown in Table 1, biphenyl product was detected in 69-75% yield when the reaction was carried
out in toluene, tetrahydrofuran (THF) and EtOH (Table 1, entries 1-3). The better conversion of
biphenyl was observed for H2O/EtOH (92% yield for entry 4). When H2O was used as solvent,
an excellent yield (97%) was detected (Table 1, entries 5 and 6). K2CO3 was used as base for
optimizing the conditions of reaction. Table 1 illustrates the effect of catalyst molar ratio on the
conversion time of bromobenzene as typical substrate at 80 °C in water. The optimum amount of
the catalyst was found to be 0.36 mol% of Pd in current conditions (Table 1, entries 5-7).
Table 1 Suzuki-Miyaura coupling reaction in various solvents and different amount of
Pd/Fe3O4/r-GO.
K2CO3
B(OH)2
25 min
+
Pd/Fe3O4/r-GO
Br
9
Page 9 of 23

Entry
Solvent
EtOH
Catalyst (mol%)a Temp (°C) Yields%b
1
2
3
4
5
6
7
0.54
0.54
0.54
0.54
0.54
0.36
0.18
70
80
60
80
80
80
80
75
92
74
69
97
97
90
H2O/EtOH (1:1)
THF
toluene
H2O
H2O
H2O
a Mol% of Pd.
b Isolated yields.
As shown in Table 2, the Suzuki-Miyaura reaction of various aryl halides, even aryl chloride,
was examined under optimal reaction conditions to show the high catalytic activity of magnetic
Pd/Fe3O4/r-GO nanohybrid. Suzuki-Miyaura reactions of deactivated aryl chloride including
chlorobenzene and 2-chloropyridine proceeded with high yields of 85% and 88%, respectively,
(Table 2, entries 4 and 7). The Suzuki reaction of activated aryl chlorides with different
substituents also gave good yields, (Table 2, entries 5 and 6). In addition, the Suzuki reaction of
aryl iodide and bromides produced excellent yields, (Table 2, entries 1-3). Usually, aryl chloride
is less reactive than aryl bromide and aryl iodide in cross-coupling reactions due to its stronger
C(sp2)-Cl bond than that of C(sp2)-Br and C(sp2)-I. Also, the electron-deficient aryl halide is
generally more active than the electron-rich one [28]. This observed fact presumably is held for
the reaction with the oxidative addition process as the rate-determining step.
Table 2 Suzuki-Miyaura reaction between aryl halides and phenyl boronic acid in the presence
of Pd/Fe3O4/r-GO nanohybrid.
Entry
1
Substrate
C6H5I
Product
Time(h) Yieldsa%
15min
>99
1a
10
Page 10 of 23

2
3
4
5
6
7
C6H5Br
4-MeC6H4Br
C6H5Cl
25min
1.5
97
85
85
82
78
88
1a
1b
1a
1c
1d
1e
2.5
4-CNC6H4Cl
4-NO2C6H4Cl
C5H4NCl
1.5
1.5
20
a Isolated yield.
The catalytic performance of different Pd-based catalysts in the coupling of chlorobenzene
and phenyl boronic acid were shown in Table 3. Magnetic Pd/Fe3O4/r-GO nanohybrid as a
heterogeneous catalyst shows the highest performance in comparison to other catalysts. Most of
the other published procedures (Table 3) need long time and using toxic solvent with lower
isolated yield. Regardless of the exact mechanism of the reaction, high surface area of Pd,
magnetic Fe3O4 NPs and r-GO as support is expected to increase the activity of a heterogeneous
catalyst.
Table 3 Catalytic performance of different Pd-based catalysts in the coupling of chlorobenzene
and phenyl boronic acid.
Yields
(%)
Entry
Catalyst
Solvent
Base Temp(°C) Time(h)
Ref
a
1
2
3
4
5
6
7
Pd(OAc)2(1f)2
H2O/EtOH=3:2
H2O/DMF=1:1
H2O
K2CO3
K2CO3
NBu4OH
K2CO3
Cs2CO3
K2CO3
K2CO3
80
65
10
7
66
29
Pd (II)-MWCNTsb
Pd NPs-ILc
53
30
31
32
33
19
34
90
3
92
Pd (II)-SBA-16d
Pd (OAc)2/DABCOe
Pd/r-GOf
H2O/EtOH=1:9
DMF
80
12
19
3
28
110
80
65
H2O
80
g
Pd(OAc)2-Fe3O4
H2O/EtOH=1:1
80
8
45
11
Page 11 of 23

8
9
Pd NPs/PSh
H2O/DMF=1:1
H2O
Na2CO3
K2CO3
100
80
12
48
85
35
Pd/Fe3O4/r-GO
2.5
This
work
a: 2 mol% of Pd and TBAB as additive; b: Pd-Schiff base@MWCNTs (0.2 mol%); c: Pd NPs in
tetraheptylammonium bromide (2.5 mol% of Pd); d: 0.5 mol% of Pd (II)-SBA-16; e: 3 mol% of
Pd(OAc)2; f: 0.48 mol% of Pd; g: Fe3O4/SiO2-metformin-Pd(OAc)2 (0.14 mol% of Pd); h: Pd
NPs on styrene-divinylbenzene polymer (0.5 mol% of Pd).
From industrial point of view, the reusability of the catalyst is important for the large scale
operation. Therefore, the reusability of the catalyst was examined in the reaction of
°
bromobenzene with phenyl boronic acid at 80 C in water. Since the catalyst can be separated
from reaction mixture using external magnetic field, therefore it recovered with a simple magnet
after dilution of the reaction mixture with CH2Cl2. The results showed that the catalyst can be
reused eighth consecutive times without noticeable losing activity (Figure 4). The recovered
catalyst was dried and checked with XRD analysis. Pd/Fe3O4/r-GO nanohybrid catalyst showed
no significant change in magnetic property and reactivity after using the catalyst for eight times.
These results show that reaction of bromobenzene with phenyl boronic acid occurred on
heterogeneous Pd/Fe3O4/r-GO nanohybrid. Furthermore, the amount of Pd NPs after eighth
consecutive runs was determined (0.31 mol% of Pd).
100
80
60
40
20
0
1
2
3
4
5
6
7
8
Run
12
Page 12 of 23

Figure 4. Reusability of Pd/Fe3O4/r-GO nanohybride in the synthesis of biphenyl from
bromobenzene and phenyl boronic acid.
4. Conclusion
In conclusion, we have demonstrated that Palladium NPs supported on an efficient magnetic
Fe3O4/GO nanohybrid by reduction of dichloropalladium complex (II) in water. The magnetic
Pd/Fe3O4/r-GO as heterogeneous catalyst exhibits high catalytic activity in the Suzuki-Miyaura
cross-coupling reaction in water. However, a series of biaryl derivatives were obtained in
moderate to excellent yield in mild conditions from the reaction of phenyl boronic acid with aryl
bromides or chlorides derivatives. Additionally, the unique catalyst can be easily separated from
the reaction mixture by simple magnetic attraction.
Acknowledgment
We thank the Yasouj University Research Council for financial support. Also, we would like
to thank the Iranian Nanotechnology Initiative Council for their support.
References
[1] (a) L.X. Yin, J. Liebscher, Chem. Rev. 107 (2007) 133–173; (b) A.K. Diallo, C.
Ornelas, L. Salmon, J.R. Aranzaes, D. Astruc, Angew. Chem. Int. Ed. 19 (2007) 8644-
8648; (c) A. Fihri, M. Bouhrara, B. Nekoueishahraki, J.M. Basset, V. Polshettiwar,
Chem. Soc. Rev. 40 (2011) 5181–5203.
[2] (a) G. Park, S. Lee, S.J. Son, S. Shin, Green. Chem. 15 (2013) 3468-3473; (b) G.M.
Scheuermann, L. Rumi, P. Steurer, W. Bannwarth, R. Mulhaupt, J. Am. Chem. Soc. 131
(2009) 8262-8270; (c) S.K. Beaumont, J. Chem. Technol. Biotechnol. 87 (2012) 595-
600.
[3] (a) A. Balanta, A. C. Godard, C. Claver, Chem. Soc. Rev. 40 (2011) 4973–4985; (b)
N.T.S. Phan, M. Van Der Sluys, C.W. Jones, Adv. Synth. Catal. 348 (2006) 609–679.
13
Page 13 of 23

[4] (a) A.H. Lu, E.L. Salabas, F. Schuth, Angew. Chem. Int. Ed. 46 (2007) 1222-1244; (b)
J. Perez, M. Nat, Nanotechnol. 2 (2007) 535-536; (c) S.H. Sun, C.B. Murray, D. Weller,
L. Folks, A. Moser, Science 287 (2000) 1989-1992; (d) J. Gao, W. Zhang, P. Huang, B.
Zhang, X. Zhang, B. Xu, J. Am. Chem. Soc. 130 (2008) 3710-3711.
[5] (a) S. Sun, H. Zeng, J. Am. Chem. Soc. 124 (2002) 8204-8205; (b) A.H. Latham, M.E.
Williams, Acc. Chem. Res. 41 (2008) 411-420; (c) S. Laurent, D. Forge, M. Port, A.
Roch, C. Robic, L.V. Elst, R.N. Muller, Chem. Rev. 108 (2008) 2064-2110.
[6] (a) M.-J. Jin, D.-H. Lee, Angew. Chem. Int. Ed. 49 (2010) 1119-1122; (b) T. Zeng, W.
Chen, C.M. Cirtiu, A. Moores, G. Song, C. Li, Green Chem. 12 (2010) 570-573; (c) B.
Sreedhar, A.S. Kumar, P.S. Reddy, Tetrahedron Lett. 51 (2010) 1891-1895; (d) H.Y. Lu
, S.H. Yang, J. Deng, Z.H. Zhang, Aust. J. Chem. 63 (2010) 1290-1296; (e) F. Shi, M.K.
Tse, S. Zhou, M.M. Pohl, J. Radnik, S. Hubner, K. Jahnisch, A. Bruckner, M. Beller, J.
Am. Chem. Soc. 131 (2009) 1775-1779; (f) S.J. Hoseini, H. Nasrabadi, M. Azizi, A.
Salimi-Beni, R. Khalifeh, Synth. Commun. 43 (2013) 1683-1691; (g) M. Nasr-Esfahani,
S.J. Hoseini, M. Montazerozohori, R. Mehrabi, H. Nasrabadi, J. Mol. Catal. A: Chem.
382 (2014) 99-105.
[7] A. Taher, J.B. Kim, J.Y. Jung, W.S. Ahn, M.J. Jin, Synlett (2009) 2477-2482.
[8] H. Firouzabadi, N. Iranpoor, M. Gholinejad, J. Hoseini, Adv. Synth. Catal. 353 (2011)
125-132.
[9] A.K. Geim, K.S. Novoselov, Nat. Mater. 6 (2007) 183-191.
[10] F. Scherer, M. Anton, U. Schillinger, J. Henkel, C. Bergemann, A. Kruger, B.
Gansbacher, C. Plank, Gene Ther. 9 (2002) 102-109.
14
Page 14 of 23

[11] W. Gersting, U. Schillinger, J. Lausier, P. Nicklaus, C. Rudolph, C. Plank, D.
Reinhardt, J. Rosenecker, J. Gene Med. 6 (2004) 913-922.
[12] M. Muthana, S.D. Scott, N. Farrow, F. Morrow, C. Murdoch, S. Grubb, N. Brown, J.
Dobson, C.E. Lewis, Gene Ther. 15 (2008) 902-910.
[13] (a) W.H. Shi, J.X. Zhu, D.H. Sim, Y.Y. Tay, Z.Y. Lu, X.J. Sharma, Y.Zhang, M.
Srinivasan, H. Hang, H.H. Hng, Q.Y. Yan, J. Mater. Chem. 21 (2011) 3422-3427; (b)
X.Y. Yang, Y.S. Wang, X. Huang, Y.F. Ma, Y. Huang, R.C. Yang, H.Q. Duan, Y.S.
Chen, J. Mater. Chem. 21 (2011) 3448-3454.
[14] N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457-2483.
[15] C. Xu, X. Wang, J.W. Zhu, X.J. Yang, L.D. Lu, J. Mater. Chem. 18 (2008) 5625-5629.
[16] M. Trilla, R. Pleixats, M.W.C. Man, C. Bied, J.J.E. Moreau, Adv. Synth. Catal. 350
(2008) 577-590.
[17] G. Bringmann, R. Walter, R. Weirich, Angew. Chem. 29 (1990) 977-991.
[18] (a) K. Mori, K. Yamaguchi, T. Hara, T. Mizugaki, K. Ebitani, K. Kaneda., J. Am.
Chem. Soc. 124 (2002) 11572-11573; (b) H. Lebel, M.K. Janes, A.B. Charette, S.P.
Nolan, J. Am. Chem. Soc. 126 (2004) 5046-5047.
[19] S.J. Hoseini, M. Dehghani, H. Nasrabadi, Catal. Sci, Technol. 4 (2014) 1078-1083.
[20] (a) W.S. Hummers, R.E. Offeman, J. Am. Chem. Soc. 80 (1958) 1339-1339; (b) H.
Yang, F. Li, C. Shan, D. Han, Q. Zhang, L. Niu, A. Ivaska, J. Mater. Chem. 19 (2009)
4632-4638.
[21] A. Gomathi, S.J. Hoseini, C.N.R. Rao, J. Mater. Chem. 19 (2009) 988-995.
[22] H.A. Becerril, J. Mao, Z. Liu, R.M. Stoltenberg, Z. Bao, Y. Chen, ACS Nano. 2 (2008)
463-470.
15
Page 15 of 23

[23] D. Li, M.B. Muller, S. Gilje, R.B. Kaner, G.G. Wallace, Nat. Nanotechnol. 3 (2008)
101-105.
[24] H. Yang, C. Shan, F. Li, D. Han, Q. Zhang, L. Niu, Chem. Commun. (2009) 3880-3882.
[25] A.J. Patil, E. Muthusamy, S. Mann, Angew. Chem., Int. Ed. 43 (2004) 4928-4933.
[26] H. Firouzabadi, N. Iranpoor, A. Ghaderi, M. Ghavami, S.J. Hoseini, Bull. Chem. Soc.
Jpn. 84 (2011) 100-109.
[27] Y. Si, E. T. Samulski, Chem. Mater. 20 (2008) 6792-6797.
[28] G. Wei, W. Zhang, F. Wen, Y. Wang, M. Zhang, J. Phys. Chem. C. 112 (2008) 10827-
10832.
[29] S. Li, Y. Lin, J. Cao, S. Zhang, J. Org. Chem. 72 (2007) 4067-4072.
[30] M. Navidi, N. Rezaei, B. Movassagh, J. Organomet. Chem. 743 (2013) 63-69.
[31] M.H.G. Prechtl, J.D. Scholten, J. Dupont, Molecules. 15 (2010) 3441-3461.
[32] S. Wei, Z. Ma, P. Wang, Z. Dong, J. Ma, J. Mol. Catal. A: Chem. 370 (2013) 175-181.
[33] J.H. Li, Q.M. Zhu, Y.X. Xie, Tetrahedron. 62 (2006) 10888-10895.
[34] M. Beygzadeh, A. Alizadeh, M.M. Khodaei, D. Kordestan, Catal. Commun. 32 (2013)
86-91.
[35] K. Karami, M. Ghasemi, N. Haghighat Naeini, Catal. Commun. 38 (2013) 10-15.
Graphical Abstract
Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable
catalyst for Suzuki-Miyaura coupling reaction in water
S. Jafar Hoseini, Vahid Heidari and Hasan Nasrabadi
Palladium nanoparticles supported successfully on an efficient magnetic Fe3O4/graphene oxide
nanohybrid by reduction of dichloropalladium complex in water. Pd/Fe3O4/reduced-graphene
oxide nanohybrid was suitable for Suzuki-Miyaura carbon-carbon coupling reaction.
16
Page 16 of 23

Highlights
 Palladium NPs supported on an efficient magnetic Fe3O4/GO nanohybrid.
 Magnetic Pd/Fe3O4/r-GO shows high catalytic activity in the Suzuki-Miyaura reaction.
 Catalyst can be separated from the reaction mixture by simple magnetic attraction.
Supplementary Data
Magnetic Pd/Fe3O4/reduced-graphene oxide nanohybrid as an efficient and recoverable
catalyst for Suzuki-Miyaura coupling reaction in water
S. Jafar Hoseini,* Vahid Heidari and Hasan Nasrabadi
Analytical data for compounds
17
Page 17 of 23

Figure S1. FTIR spectra of (a) GO, (b) Fe3O4/APTES and (c) Fe3O4/APTES/GO.
°
°
Biphenyl (1a) [1], White solid, mp: 66-69 C (lit. mp 69-71 C); FT-IR (KBr/cm-1): 3058,
3032, 1568, 1479, 1424, 1344, 1168, 1090, 1040, 1005, 725, 696; 1H NMR (400 MHz, CDCl3): δ
= 7.46 (m, 2H), 7.55 (m, 4H), 7.71 (m, 4H).
18
Page 18 of 23

Figure S2. 1H NMR spectrum of biphenyl (1a) in CDCl3
°
°
4-Methylbiphenyl (1b) [2], White solid, mp: 43-44 C (lit. mp 44-46 C); FT-IR (KBr/cm-1):
1
3060, 2959, 2928, 1600, 1463, 1380, 1273, 1122, 1072, 1039; H NMR (400 MHz, CDCl3): δ =
2.45 (s, 3H, CH3), δ = 7.33 (m, 2H), 7.37 (m 1H), 7.59 (m, 2H), 7.76 (m, 2H), 7.88 (2H).
19
Page 19 of 23

Figure S3. 1H NMR spectrum of 4-methylbiphenyl (1b) in CDCl3
°
°
4-phenylbenzonitrile (1c) [3], White solid, mp: 84-86 C (lit. mp 84-88 C); FT-IR (KBr/cm-1):
1
3076, 3023, 2930, 2924, 2250, 1660, 1493, 1441, 1179, 1024, 845, 700; H NMR (400 MHz,
CDCl3): δ = 7.53 (m, 3H), 7.63 (m 2H), 7.83 (m, 2H), 8.23 (m, 2H).
20
Page 20 of 23

Figure S4. 1H NMR spectrum of 4-phenylbenzonitrile (1c) in CDCl3
°
°
4-nitrobiphenyl (1d) [4], Yellow solid, mp: 111-113 C (lit. mp 113-115 C); FT-IR (KBr/cm-1):
1
3053, 2922, 1602, 1522, 1476, 1446, 1341, 1307, 1087, 1012, 846, 743; H NMR (400 MHz,
CDCl3): δ = 7.47 (m, 3H), 7.67 (m 2H), 7.77 (m, 2H), 8.46 (m, 2H).
21
Page 21 of 23

Figure S5. 1H NMR spectrum of 4-nitrobiphenyl (1d) in CDCl3
2-phenylpyridine (1e) [4], Colorless oil, FT-IR (KBr/cm-1): 3061, 3033, 1740, 1586, 1476, 1449,
1260, 1151, 1094, 1020,799, 745, 687; 1H NMR (400 MHz, CDCl3): δ = 6.89 (m, 1H), 7.28 (m,
1H), 7.32 (m, 2H), 7.37 (m, 1H), 7.45 (m, 1H), 7.96 (m, 2H), 8.56 (m, 1H).
22
Page 22 of 23

Figure S6. 1H NMR spectrum of 2-phenylpyridine (1e) in CDCl3
References:
[36] N.S. Nandurkar, B.M. Bhange, Tetrahedron. 64 (2008) 3655-3660.
[37] D.W. Old, J.P. Wolfe, S.L. Buchwald, J. Am. Chem. Soc. 120 (1998) 9722-9723.
[38] O. Grossman, D. Gelman, Org. Lett. 8 (2006) 1189-1191.
[39] C. Desmarets, R. Omar-Amrani, A. Walcarius, J. Lambert, B. Champagne, Y. Fort, R.
Schneider, Tetrahedron. 64 (2008) 372-381.
23
Page 23 of 23